Mineral oil composition and improving agent therefor



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PATENT J OFFiCE MINERAL OIL COMPOSITION AND IltflROVING AGENT THEREFOR Orland M. Reiff and Ferdinand P. Otto, Woodbury, and John J. Giammaria, Riverside, and Edward A. Oberright, Woodbury, N. J., assignors to Socony-Vacuum Oil Company, Incorporated, New York, N. Y., a corporation of New York No Drawing. Application October 18, 1939,

Serial No. 300,010

30 Claims.

This invention has to do in a general way with mineral oil compositions and is more particularvly related to mineral oil compositions of the viscous type used as lubricants, transformer oils and the like to which an agent has been added for the purpose of improving the oil in certain re- 'spects. It is an object of this invention to provide a novel class of improving agents for use in mineral oil fractions and further to provide mineral oil compositions containing such improving agents.

It is well known to those familiar with the art that mineral oil fractions refin'ed for their various uses are in and of themselves usually deficient'in one or more respects so that their pracoil fractions refined for use as lubricantshav'e 'a tendency to'oxidize under their conditions of use with the formation of products such as sludge, acid and the like. Motor lubricants, for example,

- under the conditions of use encountered in an products.

In this same regard certain oils, depending upon their method of refining, such for example as oils which have been refined by solvent-extraction methods to a high viscosity index, have a tendency under the conditions of use encountered in. internal combustion engines and the like to corrodecertain types of alloy metals such as the cadmium-silver alloys of the type used in hard metal bearings. Other improving-agentsare added to oils of this type for the purpose (of inhibiting this corrosive action. I j

It is also thep-ractice to add other ingredients to mineral oil fractions for the purpose of improving their oiliness characteristics, particularly when the oils are used for the purpose of lubricating metal surfaces engaged under extremely high pressures and at high rubbing speeds. Other ingredients have been developed for. the purpose of depressing the pour point of refined viscous mineral oil fractions, and still other ingredients are added to oil fractions of this type to improve their viscosity index.

The various ingredients which have been developed fOr use in mineral oil fractions to improve them in the several respects enumerated 5 above are largely specific in their particular applications, and it has therefore been the practice to add a separate ingredient for each of the improvements to be effected- It isa primary object of this invention to providea class of mineral oil-improving'agents which aremuIti-functional inltheir' properties so that by the'use of a single such" ingredient a min- "ei'al oil fraction may'be" improved in two or. more of the unrelatedproperties enumerated above.

to provide viscous? mineral oil compositions wherein this multifunctional improvement .has beemeffected through the use of one of the compounds or condensation 'products contemplated The compounds-or condensation products contemplated herein as mineral oil-improving agents may be broadly designated as the 'imetal'salts'of alkylated or alkyl-substituted aromatic-aliphatic carboxylic acids in" which 'the alkyl 'substituent has at least 20 carbon atoms and is attached to the aromatic nucleus.

We are aware of the fact that it has previously been proposed: to add certain metal salts of certain organic acids to mineral oils for the .pur-. pose of effecting specific-improvements therein. For example, calcium=phenyl stearate or a mixture of calcium phenyl stearate and calcium stearate-has been added to motor lubricants with a view to decreasing the tendency of such lubricantstocause ring-sticking. Also, certain-lead soaps of fattyacids, and naphthenic acids have been proposed as-addition agents for mineral oils ;toimprove their load-carrying, ability. These soaps or salts, however, are; as indicated above, specific intheir action and do not have the multifunctional-properties characterizing the metal- .organic compounds contemplated by the present invention. These multifunctional properties, we have discovered, are obtained by combining in a single compound or condensation product a char acterizing aromatic nucleus having one or more heavy alkyl substituents containing at least 20 carbon atoms and in addition having a hydrogen atom of the aromatic nucleus substituted with an aliphatic or cycle-aliphatic metal carboxylate group.

The aromatic nucleus characterizing the compounds contemplated by this invention may be either monoor poly-cyclic, and it may contain .tical uitility is"limited evenin'the field for which n m -s -still further objec't. "of thisinvention they have been refined. Forexample, mineral substituents other than the two types mentioned above. For example, the aromatic nucleus may be a monoor polycyclic aromatichydrocarbon nucleus in which at least one of the nuclear hydrogen atoms is substituted with a radical selected from the group consisting of: hydroxyl, alkoxy, aroxy, aralkyl, aryl, alkaryl, halogen, nitro, amino and organic ester radicals and alkyl groups containing less than 20 carbon atoms. It is to be understood that the term aromatic as used herein is intended in its broad sense to include aryl nuclei having substituents of the general type classified above. Of these various substituted aromatic nuclei special preference is given to compounds of the general type indicated above in which at least one hydrogen atom of the characterizing aromatic nucleus is substituted with a hydroxyl radical.

In order to obtain the multifunctional properties which characterize the oil-improving agents contemplated herein, we have found that the socalled heavy alkyl'substituent should contain at least 20 carbon atoms. These high molecular weight aliphatic substituents may be derived from pure or substantially ,pure aliphatic hydrocarbon compounds or they may be derived from a mixture predominantly comprised of these high molecular weight aliphatic hydrocarbons containing at least 20 carbon atoms. Such a mixture is typified .by petroleum waxes such as paraflin wax, which because of its availability and the ease with which; the compounds may be synthesized therefrom is considered as a preferred source for the' heavy-"alkyl substituents in the oil-improving agents contemplated herein.

Since the miscibility or solubility of these oilimpr'oving agents, 'andparticularly their multifunctional properties, are controlledor governed by the heavy alkyl substituent, the extent to which the aromatic nucleus is substituteduwith these heavy alkyl 'groupssbecomes anl import'ant factor in obtaining products having the desired properties. This degree of substitution in the aromatic nucleus will vary more or less depending upon the aliphatic hydrocarbon group which carries the carboxylate radicalthat is, whether such group is a short or long chain chain hydrocarbon groupand will also vary depending upon whether or not the aromatic nucleus is monoor polycyclic and whether such nucleus carries other substituents. In general it may be said, however, that the aromatic nucleus should have at least one of the nuclear hydrogen atoms substituted with an aliphatic hydrocarbon group containing at least 20 carbon atoms, and it is preferable that the average composition of these complex salts should be such that the aromatic nucleus carries two or three heavy alkyl groups. In case the aliphatic constituent in the alkyl carboxylate radical is of high molecular weightthat is, of the type derived from stearic acid-the degree of heavy alkyl or "wax-substitution may be less than is required to give the same multifunctional properties to a compound in which the alkyl carboxylate group is derived from a low molecular weight acid such as acetic acid.

Another important factor to be observed in connection with the oil-improving agents contemplated herein is that the heavy alkyl group, particularly when such group is derived from petroleum wax, may be either monoor polyvalent. In other words, such group may be in the nature of a long free chain attached to the aromatic nucleus or it may be a long aliphatic chain to which several of the aromatic-aliphatic carboxylate groups are attached. In the event several of these'nuclei are attached to a single paraifin wax hydrocarbon chain, for example, it will be seen that the solubilizing effect of the aliphatic group is distributed among the several nuclei, and we have found that a mineral oilimproving agent of the desired properties is not obtained if the composition is predominantly comprised of compounds in which more than four of the aromatic-alkyl carboxylate complexes are attached to a single long chain hydrocarbon radical.

It is also to be understood that if the so-called polyvalent high molecular weight aliphatic hydrocarbon groups are present, each aromatic complex may carry several of such groups, which in turn may be combined with other aromatic complexes to form a condensation product of a lattice type, wherein from 2 to 4 of the aromatic.- alkyl carboxylate nuclei are interconnected by two or more aliphatic hydrocarbon chains of 20 or more carbon atoms. I

The alkyl carboxylate group,-which constitutes the -other characterizing substituenty-in the aromatic nucleus of the mineral oil-improving agents contemplated herein, may be either aliphatic or cyclo-aliphatic and. may. be derived from the corresponding organic acids of various molecular weights. In this regard it 151150. be understood that the termalkyl or aliphaticpwhen used herein in connection with the .alkyls-car+ boxylate group, hasmeference -.-to both aliphatic and cycle-aliphatic radicals, andthat'this alkyl .carboxylate group may contain at least 0ne:-Substituent selected from-the group-consistingaof-r alkyl, aralkyl, alkaryharyl, keto, ether, hydroxyl, halogen, nitro, and amino radicals; Also, this alkyl carboxylate group maybe monoor polybasic; and in (the event-it is-poly basic, it is to be understood thatall of the carboxyl -groups are substituted with metal.

As to the metal substituent ;.in the carboxyl group of the compounds contemplated herein,'it

appears that any metal may be usedto provide a salt having additional properties on-improved properties, as compared with the corresponding acid. The metals contemplated herein may-be broadly classified .as metals of groups-'oneto eight inclusive of the periodic system'which are capable of formingcarboxylate salts. -"I'hese metals comprise the following: the alkalimetals: lithium, sodium,- potassium,- rubidium' and caesium; the alkaline earth-group: beryllium, magnesium, calcium, strontium and barium; the .metals. zinc, cadmium, mercury seandium, yttrium, lanthanum; aluminum gallium, indium, thallium, titanium, "zirconium, cerium t orium; germanium, tin andlead; vanadium, columbiurn and tantalum; arsenic, antimony and bismuth; chromium, molybdenum, tungsten'and uranium; rhenium, manganese, iron, cobalt" and nickel; ruthenium, rhodium and palladium;""osmium, iridium and platinum. Some of the rare earth metal'sare given in the foregoing. Other rare earth'metals suitable "for the formation of metal'salts of aryl aliphatic acids are those now commercially available as the cerium and yttrium group: namely, a mixture of praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thallium and luteciumg Although, as indicated above, any of the foregoing metals may be used to provide a mineral oil-improving agent falling into the general class contemplated herein, we have found that the salts of the alkali metals tend to form emulsions, and for this reason preference is given to salts of the polyvalent metals. The multifunctional properties of the compounds may also be varied by the selection of metals. All of the metals appear to impart antioxidant properties to the condensation products and by the use of metals such as lead and zinc, for example, improved oiliness characteristics may be obtained.

From the foregoing discussion and from the description of the preferred synthesizing procedures which will appear hereinafter, it will be seen that the specific molecular composition of the mineral oil-improving agents contemplated herein may vary over relatively wide limits, depending upon whether the aromatic nucleus is monoor polycyclic, whether it carries substituents other than the heavy alkyl group or groups and the alkyl carboxylate group, whether the condensation of the aromatic nucleus with the heavy alkyl substituent is effected with a pure compound or a mixture of aliphatic hydrocarbon compounds, etc. The composition will also vary, depending upon the aliphatic carboxylate group and whether such group is substituted or unsubstituted. In general, however, all of the compounds contemplated herein as mineral oilimproving agents, whether such compounds be existant in a pure state or in admixture with other compounds of a similar nature, may be represented by the following general formula:

In the above general formula T represents a monoor polycyclic aromatic nucleus; Z 'represents an organic radical, or more specifically an "aliphatic or' cycloaliphatic hydrocarbon group, which is substituted for one of the nuclear hydrogen atoms in the aromatic nucleus T; COOM represents at least one carboxylate group in which the carboxyl hydrogen is replaced with its equivalent weight of a metal M. This carboxylate group is attached to the'aliphatic or cyclo-aliphatic radical represented by Z. The character R, represents at least one aliphatic hydrocarbon radical of at least 20 carbon atoms having a valence v of from 1 to 4 and attached by one valence bond only to at least one aromatic nucleus T. Yb represents a monovalent radical attached to T, such radical being selected from the group consisting of residual hydrogen and hydroxyl, alkoxy, aroxy, aralkyl, aryl, alkaryl, halogen, nitro, amino and organic ester radicals and monovalent alkyl radicals containing less than 20 carbon atoms. The character b in the symbol Yb represents the number of Y1; radicals and is equal to zero or a Whole number corresponding to the replaceable hydrogen atoms on the nucleus T not substituted with R) and (Z.COOM). The subscript n represents a whole number from 1 to 4.

In the foregoing general formula representation of the oil-improving agents contemplated herein it will be seen that the compounds represented thereby include those materials in which all of the high molecular weight multifunctionalimparting substituent (R") is monovalent (17:1 and 11:1) or in which all of this heavy alkyl substituent is polyvalent (v and n being equal to 2, 3 or 4) also, since R is defined as being at least one aliphatic radical having at least 20 carbon atoms and may therefore include several such groups, it will be seen that this general formula is inclusive of compounds containing these heavy alkyl radicals of diflerent valences (from 1 to 4) VI VUV in the same molecule. Furthermore, it will be observed that since n may be any whole number from 1 to 4, the number of aromatic nuclei T in the molecule may likewise vary from 1 to 4. It will be seen, therefore, that the relationship between n and v in its broadest aspect,is such that when n is equal to 1, v is equal to 1; and when n is greater than 1, the valence v of at least one of the R s is equal to n in order to tie the sev-v eral nuclei or Ts together, the valence of any remaining R s being any whole number equal to or less than 12.

Typical compounds coming under the foregoing general formula and characterized by both monoand polycyclic aromatic nuclei may be represented by the following formulae, wherein at least one R represents an aliphatic hydrocarbon radical containing at least 20 carbon atoms and in which the remaining R"s represent radicals radicals selected from the group consisting of hydrogen, alkoxy, hydroxyl, aroxy, aralkyl, aryl, alkaryl, halogen, nitro, amino and organic ester radicals and alkyl radicals containing less than 20 carbon atoms.

A compound of the foregoing type represented in another way may be expressed by the formula:

III z.o0oM

in which the chain represents the heavy alkyl group of at least 20 carbon atoms and in which Yb represents substituents as defined above un- IV Z.OOOM

The foregoing Formulae II to IV inclusive represent the simplest types of alkyl-substituted aromatic-aliphatic carboxylates which are contemplated herein as mineral oil-improving agents. In all of these general formulae it will be observed that the heavy alkyl multifunctional-imparting substituent is monovalent, and in the general Formulae III and IV it will be observed that the aromatic nucleus carries only one such substituent.

' Since the group R has been defined in the gen eral formula as at least one and since, as pointed out above, it is preferable in most cases that the v in which the chains and the substituent characters have the same significance defined above.

It has been pointed out that the condensation products contemplated herein may be comprised of several (2, 3 or 4) of the aromatic nuclear complexes attached to one or more of the long chain aliphatic hydrocarbon radicals. Compounds of this general nature are represented by the general Formula I above wherein v and n become 2, 3 or 4. A compound of this type in which there is only one R group and in which '0 is equal to 3 may be represented by the formula:

VI 2.00011 z.oooM

Z.COOM

K compound of this type in which the several aromatienuclearcomplexes are interconnected'by several of the heavy alkyl radicals may be represented by the following formula:

. 11.. ..H, H H H Ho '0 o o --CH H H Yrb-LCOOM Yrz.oooM Yt-l- '-Z.COOM H l E E0 --o --o --o --oH H H H H n The possible molecular structure of compounds in which the aryl nucleus T is poly-cyclic will be obvious from the foregoingillustrative formulae. The I possible molecular structure of compounds in which 0 and n are equal to 2 and 4 will be readily understoodfrom the Formulae VI and VII.

Relative to the Formulae VI and VII it will be understood that the several nuclear complexes may each or all carry monovalent heavy alkyl groups in addition to the waxgroup or groups connecting them to other nuclear complexes; also the compound may be comprised of one heavy alkyl group attached to say two of the nuclear complexes and another heavy alkyl group attached to three or four of the nuclear complexes. As to the possible number of these heavy alkyl or R" groups going to make up a single molecule, this will vary with the extent to which it is desired to effect substitution of the nucleus with these multifunctional-imparting substituents. It is important, of course, as indicated above, to have the heavy alkyl or wax substituent present in sufiicient amount to impart multifunctional properties to the compound, but it is also desirable that the amount of heavy alkyl substituent in the product be not substantially greater than necessary to impart the desired pour-depressing and V. I. improving properties because a great predominance of the heavy alkyl material in the compound will act to reduce the effectiveness of the alkyl carboxylate group in a given quantity of product.

In synthesizing the oil-improving agents contemplated herein the general procedure involves first condensing a high molecular weight aliphatic hydrocarbon material with the desired aromatic compound, which, as aforesaid, may carry other substituents such as a hydroxyl group. In this condensation reaction pure or substantially pure high molecular weight aliphatic compounds may be employed; or, as has also been previously indicated, the aliphatic material may be a mixture predominantly comprised of aliphatic compounds having at least 20 carbon atoms, such a mixture being typified by parafiin wax. r The condensation may be eifected by first halogenating the aliphatic material and condensing same with the aromatic material by means of Friedel-Crafts catalytic reaction. This condensation may also be carried .out with high molecular weight unsaturated aliphatic hydrocarbons or with high molecular weight alcohols, using sulfuric acid or aluminum chloride as catalyst. Also, the high molecular weight alcohol may be converted to an alkyl halide and condensed with the aromatic material by means of the Friedel-Crafts reaction. Since paraflin wax is considered to be the preferred source for the heavy aliphatic substituent we may hereinafter refer to this alkylated aromatic condensation product as a wax-aryl compound. By, this term it is to-be understood that we include wax-aromatic compounds in which .the .aromaticnucleus' contains another or other substituents such as the hydroxyl group.

After obtaining the wax-aromatic condensation product, such product is condensed with an aliphatic or cycle-aliphatic carboxylic acid to obtain an alkylated aromatic-alkyl carboxylic acid whichcan then be neutralized with an alkali -to form the alkali salt from which salts of the Specific procedures which may be followed in effecting the condensation between the waxaromatic compound and the aliphatic acid are as follows:

(a) Condensation of alkylated aromatic or hydroxyaromatic compounds with unsaturated aliphatic acid such as oleic acid, using a so-called kationoid catalyst such as sulfuric acid, zinc chloride,'aluminum chloride, etc., to effect the addition of the nucleus.

(b) Condensation of an alkylated aromatic or hydroxyaromatic hydrocarbon with halogenated aliphatic or cyclo-aliphatic acids, such as chloracetic, chlorstearic' and chlornaphthenic acids, by means of the Friedel-Crafts reaction using anhydrous aluminum chloride as the preferred catalyst.

(cl Inthe case of acids of the type contemplated herein which contain a hydroxyl substituent in the aromatic nucleus, such acids may be prepared by a rearrangement of the corresponding alkylated aryl ether aliphatic acids in the presence of a kationoid catalyst such as I-ICl gas.

(d) Hydroxyaryl-aliphatic acids can be converted to the corresponding ether aryl-aliphatic acids by methylating the hydroxyl group by reaction with alkylating agents like dimethyl sulunsaturated acid to the aryl.

252. Cot/iron; limo.

fate or alkyl halides or by reaction with arylating agents such as aryl halides.

In the eventa compound is desired in which the aromatic nucleus contains as a substituent halogen, nitro, or amino groups, it is preferred to introduce such groups into the compound after phenol, resorcinol, hydroquinone, catechol,- cresol.

'hydroxy-diphenyl, benzylphenol, alpha-- and beta-naphthol and beta-methylnaphthol, anthranol, phenyl-methylnaphthol, etc.; and aryl ethers such as dipheny-l ether and naphthyl ether, or mixed alkyl-aryl or aralkyl-aryl ethers such as anisole, naphthylmethyl ether and benzylphenyl ether. Preference in general, as has been previously indicated, is to the monoand poly-cylic aromatic (preferably naphthalene) and to the mono-hydroxyphenols otherwise unsubstituted, particular preference being given to phenol and alpha and beta-naphthol. 1

As sources; for the heavy a1 l multifunctionalimparting subst-ituent-weprefer-to use, as has been; preili'nisiyg indicated; af'mixtm'e or' high molecular weight aliphatichydrocarbons such as characterize petroleum wax, particular preference being given to paraflin wax.

Other sources of the heavy alkyl substituent are high'molecular :weight unsaturated aliphatic hydrocarbons such as polymerized iso-butylene, dodecylene, tetra-decylene, octa-decylene, melene,

-etc., and; high molecular weightalcohols, suchas :myricyl alcohol, ceryl alcohol, etc.

'As has been previously indicated, the alkyl carboxylate. substituent maybe derived from any aliphatic or cyclo-aliphatic monoor poly-basic carboxylic acid, illustrative sources of which are acetic, benzoic, butyric,'valeric, heptylic, nonylic, palmitic and stearic acids, which typify saturated acids, and must be used as the corresponding chlor-acid in which substitution takes place at the alpha. carbon atom of. the aliphatic acid group. Other aliphatic acid substituents may be obtained by'using unsaturated carboxylic'acids of the oleic series, CnH2n--202, in which case substitutiom on the nucleus takes place at the double bond in the unsaturated acid. Halogenated cyclo-aliphatic acids such as chlor-naphthenic acid may be used to obtain compounds in which the alkylated aromatic group carries .a cycloaliphatic substituent. The term alky orfaliphatic when used herein in connection with the aliphatic carboxylate substituent is intended as inclusive of both aliphatic and cyclo-aliphatic acid groups or radicals.

The details in the procedure which may be followedin synthesizing salts of alkylated aromaticaliphatic carboxylic acids of the type contemplated herein will be best understood from the following examples of specific procedures used in synthesizing the metal salts of wax-phenol stearic acid and wax-naphthalene stearic acid. It is to be understood in this connection that these examples are for illustration only and that the procedure may be varied by varying the specific reactants and the proportions thereof.

EXAMPLE 1 PREPARATION or Wax-SUBSTITUTED HYDROXYPHENYL S'rnAmc Aon) SALTS (a) Alkylatz'on of phenol A para-inn wax melting at approximately 1". was melted and heated to about 200 F., after which chlorine gas was bubbled therethrough until the was had absorbed from 16 to 20 per cent of chlorine, such product having an average composition between a mono-chlor-wax and a di-chlor-wax or corresponding roughly to a dichlor-wax. A quantity of the chlor-wax thus obtained containing 3 atomic proportions of chlorine was heated to a temperature varying from just above its melting point to not substantially over F., and 1 mol of phenol was admixed therewith. To this mixture at a temperature of about 150 F. was added a quantity of anhydrous aluminum chloride corresponding to about 3 per cent of the weight of the chlor-wax in the mixture. The rate of addition of -the aluminum chloride should be sufliciently slow to avoid violent foaming, and during such addition it is preferable to maintain the temperature in the neighborhood of 150 F. After adding the aluminum chloride the temperature is raised, preferably to a point not over 350 F. until the emission of HCl gas has substantially ceased, thus indicating a completion of the alkylation or wax-substitution of the phenol. The product thus obtained,

,wherethe quantity of ,chlor-wax containingthree H V atomicproportions of chlorine was reacted with one mol of. phenol, may be roughly designated as a .tri-wax-phenol. A more accurate description of the product, however,-is obtained through the use of the parenthetical symbol (3-16), which in- ;dicates'thatchlor-wax of 16 per cent chlorine content was used in the reaction and that a quantity of such .chlor-wax containing 3 atomic proportions of chlorine was reacted with one mol of the phenol. This type of indication will be used herein to indicate the degree of wax-substitution .of the aryl nucleus; that is, the parenthetical expression. (A-B) will be employed, wherein A indicates the number of atomic proportions of the chlor-wax reacted with one mol of the aromatic -compound '(3 in the above case) and wherein B indicates the chlorine content of the wax or chlorinated heavy aliphatic hydrocarbon which is employed in the reaction (16 per cent in the above case). Employing this designation, then,

the product of the foregoing reaction will be in- Molecules Wax-phenol (3-16) 1 Oleic acid 1 A1013 1 The wax-phenol of the type obtained according to the foregoing procedure and the oleic acid are mixed together, after which the aluminum Search Hoom chloride is added gradually with stirring at a temperature of about F. The slow addition of the aluminum chloride is necessary to control the evolution of HCl gas. The reaction temperature is then raised to about 250 F., the mixture being held at this temperature during a two-hour period to complete the reaction. The reaction product is then washed with dilute hydrochloric acid to remove the aluminum chloride catalyst, followed by water-washing until neutral. This is followed by steam-treatment to remove any unreacted aliphatic acid. The Water-washing is carried out preferably in the presence of a diluent such as benzol or Stoddard' solvent, thereafter distilling the solvent, whereby any entrained water is removed. This is followed by introduction of superheated steam at a temperature of about 390 F. The operation of steam-treating is facilitated by vigorous stirring, the steam being passed through the mixture until the distillate shows a negligible neutralization number, indicating that all unreacted aliphatic acid in the product has been removed. When the steam treatment is finished, which may require about 10 hours, steam vapors are removed from the condensation product by blowing with a non-oxidizing gas such as nitrogen, thereby yielding an anhydrous product. The product of this reaction is wax-substituted (3-16) hydroxy-phenyl stearic acid and distinguishes from the corresponding stearic acid obtained from chlor-stearic acid in that the substitution of the stearic acid group has been effected at an intermediate point in the chain.

Following the foregoing procedure and using a poly-carboxylic acid such as maleic acid a'dicarboxylic product is obtained, in this particular case the product being a wax-substituted hydroxy succinnic acid.

Wax-hydroxy-phenyl stearic acid and waxyhydroXy-phenyl acetic acid have been prepared following the foregoing procedure by employing instead of the unsaturated acid in the oleic mixture one mol of a chlor-acid in the two cases mentioned, the acids being chlor-stearic acid and chlor-acetic acid respectively.

(c) Conversion of the wax-hydrorry-aryl aliphatic acids to the corresponding salts In preparing the metal salts from the acids obtained according to the foregoing procedure the acids are first converted to the alkali metal salts, from which the polyvalent metal salts are obtained by a double decomposition.

Because of the tendency of alkali metal salts to emulsify it is advantageous to prepare such salts in a non-aqueous medium. The alkylated hydroxyaromatic-aliphatic carboxylic acid is treated with an alkali alcoholate, preferably prepared from one of the lower alcohols such as amyl or butyl or with an alcohol solution of the alkali hydroxide, in-an amount sufl'icient to neutralize the carboxyl group. The mixture is preferably heated to a temperature of about 300 F. for approximately an hour, allowing the alcohol to distill, thus obtaining the finished product. If the alkali hydroxide is used in place of the metal alcoholate, the water of reaction is removed with the alcohol during the distilling operation.

As has been previously pointed out, the tend ency of the alkali metal salts to emulsify makes the salts of polyvalent metals preferably to those obtained from the alkali metals. The polyvalent metal carboxylates are formed by double decom-.

position of the alkali metal salt with a salt of the desired metal. The reaction can be carried out in aqueous or non-aqueous solution, but a non-aqueous medium is preferred where the aromatic nucleus of the acid has been alkylated with heavy alkyl groups such as those derived from petroleum wax.

When the reaction is carried out in aqueous medium, the preferred procedure consists in neutralizing the acid with an aqueous solution of sodium hydroxide, using phenolphthalein as an indicator, thereafter adding an equivalent amount of an aqueous solution of a salt of the desired metal, stirring the mixture at room temperature during a /2-hour period to insure completion of the reaction. A solvent such a Stoddard solvent or benzol can be used in the reaction. The product is water-washed and any diluent removed by distillation to obtain the finished product.

When preparing the salts in non-aqueous medium the preferred method involves first neutralizing the acid with an alcoholate solution of sodium hydroxide, using an amount of alkali equivalent to the carboxyl constituents in the acid, and thereafter adding an equivalent amount of alcohol-soluble salt of the desired metal. In making the cobalt salt, for example, cobalt chloride may be used. The inorganic salt can be added directly, followed by the addition of about 10 per cent of butyl alcohol or amyl alcohol (fusel oil) and refluxing for about one hour at a temperature of about 250 F. to complete the double decomposition. The product can be purified by water-washing or filtering to remove the alkali salt of reaction-thereafter obtaining the finished product by distlllingto' remove the alcohol or other diluent.

As an alternative procedure the carboxylate salt can be formed in non-aqueous medium by reacting the acid with an alcoholate of the desired metal in an amount equivalent to the carboxyl constituent and heating for about one hour at 300 F. to complete the reaction. The purification of the product can be carried out by filtration or by water-washing. .If a diluent is used in the purification process, it is removed by distillation to obtain the finished product.

EXAMPLE '2 PREPARATION S'rmmo Acm SALTs In example 1 above we have described an illustrative procedure for obtaining salts of waxsubstituted hydroxy-aryl-aliphatic acids. The

preparation of salts of wax-substituted aromaticaliphatic carboxylic acids which are otherwise unsubstituted is illustrated by the following procedure which may be followed in preparing such salts wherein the aromatic nucleus is a naphthyl group.

(a) Alkylatz'on of naphthalene Parafiin having an A. S. T. M.melting point of about 126 F. is chlorinated at a temperature of from about to 200 F. until the desired or wsx supsrrro'mb NAPHTHYIr chlorine content (as high as 20 per cent of chlorine) is obtained. The wax is chlorinated preferably to a chlorine content of about 16 per cent. A quantity of this chlor-wax which contains about 3 atomic proportions of chlorine is heated to a temperature of about 150 F., and 1 molecular equivalent of naphthalene is added thereto. Aluminum chloride is then added gradually to this mixture in the form of a slurry in a halogenated solvent such as ethylene chloride and tetrachlor-ethane. The condensation can be 252. COMPOSITIONS.

' lower temperatures a effected at the reflux temperature of the ethylene chloride, using about 3 per cent aluminum chloride based on the chlor-wax.

A suitable procedure also consists in adding the aluminum chloride to the mixture at about 250 F. in the absence otdiluents or solvents. When a diluent or solvent is not used, this higher temperature for the addition of aluminum chloride is desirable to prevent foaming of the mixture because of HCl evolution. In order to obtain products having the most effective pour-depressing action it is desirable to form a trior tetrasubstituted product. That is one in which the chlorine content of the wax and the proportions of wax and aromatic hydrocarbon are such that the aryl nucleus has 3 or 4 of its replaceable hydrogens substituted with the high molecular weight aliphatic hydrocarbon radicals.

(b) Condensation of wax-substituted naphthalene with aliphatic acids In the condensation reaction with unsaturated or halogenated aliphatic or cyclo-aliphatic acids the Friedel-Crafts mixture obtained according to the foregoing reaction may be employed without removal of the aluminum chloride catalyst. The aliphatic acid is added to the mixture, followed by addition of suficient aluminum chloride at a temperature of from to 250 F. to give at least 1 mol of aluminum chloride in the mixture for each mol of aliphatic acid. The condensation reaction is carried to completion by heating the mixture to approximately 250 F. during a 1-hour period. At reaction temperatures lower than 250 F. it is desirable to add diluents such as halogenated solvents like ethylenedichloride or tetrachlor-ethane or hydrocarbon solvents such as Stoddard solvent. At these higher concentration of catalyst or a longer reaction period is necessary, but the condensation can be carried out suitably at temperatures as low as the boiling point of ethylene dichloride (182 F.).

To illustrate this last-mentioned condensation procedure, 1 mol of wax-substituted naphthalene (3-19) and 1 mol of oleic acid are mixed together and heated to a temperature of about 150 F. 1 mol of aluminum chloride is then added to the reaction mixture with stirring to avoid too rapid evolution of HCl, and the temperature is raised to about 250 R, where it is held during a 1-hour period to complete the reaction. The reaction mixture is purified in the same manner employed for the purification of the wax-hydroxyaromaticstearic acid described in Example 1. Poly-basic alkylated aromatic-aliphatic acids can be obtalned by using unsaturated poly-basic acids such as maleic acid in the foregoing procedure, which gives an alkylated aryl succinic acid.

Wax-naphthalene alpha-stearic acid can be obtained by using the foregoing procedure anda reaction mixture consisting of 1 mol of waxsubsti'tuted naphthalene, 1 mol of chlorstearic acid, and 2 mols of aluminum chloride.

(0) Metal salts of wax-aryl-aliphatic acids EXANIPLE 3 or WAX-SUBSTITUTED ET'HER ARYL ALIIHATIC Aon) SALTS Compounds of this type in which the substituent Yb in general Formula I is an alkoxy or an PREPARATION These acids and salts can also be prepared from hydroxy-aryl-aliphatic acids of the type derived by the procedure of Example 1 by alkylating the hydroxyl group. The alkali salt of the hydroxyaryl-aliphatic acid is treated with an alkyl sulfate such as dimethyl sulfate or with alkyl or aryl halides to form the ether derivative.

These general procedures are more fully illustrated in the following examples.

(a) Condensation of wax-substituted diphenyl ether with aliphatic acid A wax-substituted diphenyl ether (3-16) was prepared following the general procedure of Example 1 (a), using one molecular proportion of diphenyl ether and a quantity of chlorinated parailin wax (16 per cent chlorine content) containing 3 atomic proportions of chlorine.

One mol of this wax-phenyl ether was mixed with one mol of oleic acid and a mol of A1013 gradually added to the mixture with stirring'at a temperature of about 150 F. The reaction was carried to completion by raising the temperature of the mixture to about 250 F. and holding at this pointduring a one-hour period.

Upon cooling'to about '150 F. the reaction inixture' was treated--wlt #water and keptacidic with aqueous HCl to removeall traces of aluminum, thereafter waterewa shing the mixture until the washings become neutral to litmus. The operation of water-washing can be facilitated by use of a diluent such as Stoddard solvent. The finished product is obtained by removal of the diluent by distillation, whereby the removal of entrained water is also effected.

When high molecular weight aliphatic acids such as oleic acid or high molecular weight cycloaliphatic acids such as naphthenic acid are used in the condensation reaction, the use of superheated steam is required for removal of unreacted aliphatic acid. This treatment is carried uct from the Friedel-Crafts chlor-wax-aryl ether condensation without isolating the intermediate product.

(b) Preparation of ether aryl aliphatic acids from hydroocy aryl aliphatic acids One mol of wax-hydroxyphenyl stearic acid (3-16) was dissolved in butyl alcohol and two atomic proportions of metallic sodium were added. The reaction mixture was heated at approximately F. for hour to form the disodium salt of wax-hydroxyphenyl stearic acid. .The reaction mixture was cooled to room temperature -.Halogenated ali- OUUI UH HUUIH Preparation of metal salts of wax-ether aryl aliphatic acid salts The metal salts of the acids obtained by the procedures of this example are prepared by following the same general procedure described above under Example 1.

EXAMPLE 4 PREPARATION or WAX-SUBSTITUTED Esme AB-YL ALIPHA'I'IC A010 SALTS Compounds of this type are those in which the substituent Yb in general Formula I is an organic ester group. They may be prepared from waxsubstituted hydroxyaromatic aliphatic acids of the type described in Example 1 by reaction with a monoor di-basic acid chloride, using AlCl3 as a catalyst. This reaction yields what we may term the ester (corresponding to the acid chloride) of the wax-hydroxyaromatic aliphatic carboxylic acid, such for example as the phthalyl ester of wax-'hydroxyphenylstearicacid 3-16). The-- 7 corresponding salts are obtained by following the general procedure described in Example 1.

To demonstrate the eifectiveness of the compounds or condensation products contemplated herein as mineral oil-improving agents we have conducted several comparative tests with representative mineral oils alone and with the same oils blended with the improving agents contemplated herein. The results of such test are discussed and listed below. 7

EXAMPLE POUR Ponv'r DEPRESSION Metal salts of the alkylated or wax-substituted aromatic acids typified by the foregoing examples are effective pour point depressants, as indicated by the results tabulated in Tables I and 11 below, in which the oils were motor oils having an A. S. T. M, pour point of +20 F.

Table I Depressant blended with motor oil of Say- Pe O rcent A.S.'I.M.- lgglitlzigfcoiay 01; :15 sec. at 210 F. and pour m oil pour tests Nickel-carboxylate salt of wax-substituted Per cent F.

(3-19) hydroxyphcnyl stearic acid y --20 D 520 15 562 +5 Table II Depressant blended with motor oil 01 Saybolt viscosity of 67 seconds at 210 F. and Per cent A. S. T. M pour point of +20 F. in oil pour tests Per cent Cobalt-carboxylate salt of wax-substituted (3-16) hydroxyphenyl stearic acid 54 -20 Nickel-carboxylate salt of wax-substituted (3-19) hydroxyphenyl stearic acid $4 20 Cobalt-carboxylate salt of wax-substituted (3-16) hydroxyphenyl stearic acid 1t 5 and one mol of dimethyl sulfate added. After Depressant blended with motor oil of Saybolt viscosity of 67 seconds at 210 F. and pour point of +20 F.

Per cent in oil Per cent Table III Depressant blended'with motor oil of Saybolt viscosity of 164.5 sec. at 100 F. and pour point of +20 F.

Per cent in oil Per cent F. Cobalt-carboxylate salt of wax-substituted (3-16) phenoxy'phenyl stearic acid Cobalt-carboxylate salt of wax-substituted (3-16) phenoxyphenyl alpha-stearic acid... Cobalt-carboxylate salt of wax-substituted (3-16) phenoxyphen lcapric acid. Oobalt-carboxylate t of wax-sub d (3-16) methoxyphenyl stearic acid. Cobalt-carboxylate salt of wax-substituted (3-16) chlorphenoxyphenyl carpic acid.

Table IV V. I. IMPROVEMENT Saybolt visc.

Compound blended with motor Code. by

oil weight 100 F. 210 F. V. I.

None Oobalt-carboxylate salt of waxsubstituted (3-16) hydroxyhenyl alpha-stoaric acid 1 N ckel-carboxylate salt of waxsubstituted (3-19) hydroxy- 'phenyl stearic acid 1 Cobaltcarboxylate salt of waxsubstituted (3-16) hydroxyphenyl acetic acid 1 Cobalt-carboxylate salt of waxsubstituted (2-19) naphthyl stearic acid Nickel-carboxylate salt of waxsubstituted (2-19) naphthyl stearic acid Cobalt-carboxylate salt of waxsubstituted (3-19) naphthyl stearic acid Nickel-carboxylate salt of waxsubstltutcd (3-19) naphthyl stearic acid 1 Cobalt-carboxylate salt of waxsubstituted (3-16) naphthyl succinic acid Vanadyl-carboxylate salt of waxsubstituted (3-14) hydroxyphenyl stearlc acid 1 Stannous-carboxylate salt of waxsubstituted (3-14) hydroxyphenyl stearic acid 1 2521 I IUNDi E JEYEQC f Q uu bll Huuui shim l'rlivtbez Table V the improving agents contemplated herein are multifunctional in their behavior and that they saybgltvisq may be added to a mineral oil to improve the p und blen gle with motor Cag same in various unrelated properties. The

1 F. a v 1 amount of improving agent used may be varied, 5

depending upon the mineral oil fraction with P cm which it is blended and the properties desired in gg 140-9 the final composition. For example, these agents substituted 3-i 6 phenoxymay be used in amounts ranging from about 1 g gggggggigggg g- 1 151-0 per cent to about 10 per cent, and in general 10 substituted s-1t) phenoxymineral oil compositions of the desired improved gggg fgfgggfg 1 7 42 6 5 properties may be obtained with these improving substituted (ii-1 6) phenoxyagents in amounts of from "1 per cent to l per 'ott iititiifgitt simta 1 Cent substituted ao phenoxy- It is to be understood that while we have here- 15 gg g gg gggg ggg 1 in described certain preferred procedures which substituted (3-l 6) methoxymay be followed in the preparation of wax-subggg tggig ggggg 1 153'? stituted aromatic-aliphatic carboxylic acid salts substituted ss phenoxyr and have referred to various representative rentiiiitifffffiiiiiijji31:31: 1. i332? iii 331:? t nts i h may be employed in providing the oggglllgigrtitrgstilrylgitew constituents for such salts, such procedures and tuted (3 1s hydmxyphenyl A reactants have been used for illustrative purposes Swarm 801d 1 1535 428 only. The invention, therefore, is not to be on sidered as limited by the specific examples givenbut EXAMPLE 7 includes within its scope such changes or modi- OPERATION TEST fications as fairly come within the spirit of the l appended clalms.

In addition to the foregoing tests we have also We claim: made 9 0115 011 blends contammg 1. An improved mineral oil composition comresentatlve Emprovmg of the con/56m prising a viscous mineral oil fraction having adplated herein to determine the effectiveness of mixed therewith a minor proportion of a metal these improvi g a en 13 the known tendency salt of an alkyl-substituted aromatic-aliphatic F 011 cause nrfg'stjlckmg F sludge depo" carboxylic acid in which the alkyl substituent is s tion during ODera In an Internal combus' attached to the aromatic nucleus and is derived tmngfmglneeeifle from an aliphatic hydrocarbon having at least- ThlS testwas carried out in a single cylinder twenty carbon atoms CFR engme whlch was operated 2. An improved mineral oil composition comdt speed of 1200 over a tune {ntetval prising a viscous mineral oilfraction having ad- 28 hours- The temperature of the coohflg mixed therewith a minor proportion of a metal (1min forthe engme was held at appmxlmatelfij salt of an alkyl-substituted aromatic-aliphatic 40 390 and the 011 temperature was held $5,150 carboxylic acid in which the alkyl substituent is F dufmg the test The on 1 a lubncat' attached to the aromatic nucleus and is derived mg o l stock of 120 sec. Saybolt viscosity at 210 F., from an aliphatic hydrocarbon having at least 2: fi gg ggz gizg i i' gfi 33 2: twenty carbon atoms, the said aromatic nucleus p 8 containing at least one hydroxyl substituent. rings were StllCfl, (b) the extent to which the 3 An improved mineral oil composition Slots i the on rings were fined with carbonacequs prising a viscous mineral oil fraction having adgfag g g 3:2 g g?; ;i $:;gg: mixed therewith a minor proportion of a mixture immber N) of the on. The results from of metal salts of alkyl-substituted aromatic-alithese tests for representative compounds of the phatic carboxylic acids m Whmh w alkyl type described above are set forth in Table VI stituents are attachedto the aromatic nuclei, said below alkyl substituents being radloals derived from Table VI petroleum waxand being predominantly rad1cals of at least 20 carbon atoms. Ring condition 4. An improved mineral oil composition comprising a viscous mineral oil fraction having ad- Percent I mixed therewith aminor proportion of a mixture Oil Degrees stuck slots Deposits N. N. of metal salts of alkyl-substituted aromatic-alifined phatic carboxylic acids in which the alkyl substituents are attached to the aromatic nuclei, said 1 2 a 4 a 3 4 5 alkyl substituents being derived from petroleum A 180 240 360 360 0 m m 5 12.84 1.3 wax and being predominantly radicals of at least o 0 0 o o 0 0 5.72 0.7 20 carbon atoms, the said aromatic nuclei each 3 3 g 8 8 3 8 3 2 5:2 containing at least one hydroxyl substituent. g g g g g g 8 5. An improved mineral oil composition comprising a viscous mineral oil fraction having ad- Ammanh mixed therewith a minor proportion of a metal Oil A =Oil A bal -car xy atc sa t or ax-s bst tuted I salt of an alkyl-substituted aromatic-aliphatic on g ifgi" naphthylstearcacd' carboxylic acid in which the alkyl substituent is Oil B =Oil liq-W730ivouad i-oarbos iotesaltoiwax-substituted attached to the aromatic nucleus and is derived u (3'14)hydmxyphenylsmflcacid from an aliphatic hydrocarbon having at least 8H g -l-UZ, cobaltous-carboxylatc salt ofwax substitutcd wenty carbon atoms, the Said aromatic nucleus (3-16) phenoxyphenyl stearicacidcontaining at least one substituent selected from the group consisting of hydroxy, alkoXy, aroxy,

From the foregoing data it will be observed that aralkyl, aryl, alkaryl, halogen, nitro, amino and organic ester radicals and alkyl radicals containing'less than twenty carbon atoms.

6. An improved mineral oil composition comprising a viscous mineral oil fraction having admixed therewith a minor proportion of a mixture of metal salts of alkyl-substituted aromatic-aliphatic carboxylic acids in which the alkyl substituents areattached to the aromatic nuclei, said alkyl substituents being derived from petroleum wax and being predominantly radicals of at least 20 carbon atoms, the said aromatic nuclei each containing at least one substituent selected from the group consisting of hydroxy, alkoxy, aroxy; aralkyl, aryl, alkaryl, halogen, nitro, amino and organic radicals and alkyl radicals containing less than 20 carbon atoms.

'7. An improved mineral oil composition comprising a viscous mineraloil fraction having admixed therewith a minor proportion of an aromatic condensation product comprising an arcmatic nucleus in which at least one nuclear hydrogen atomis substituted with a radical selected from the-group consisting of aliphatic and cycle-aliphatic corboxylic acid radicals wherein the carboxyl hydrogen is replaced with its equivalent weight of metal; and in which at least one other nuclear hydrogen atom of said characterizing aromatic nucleus is substituted with an aliphatic hydrocarbon radical of at least twenty carbon atoms.

8. An improved mineral oil composition comprising a viscous mineral oil fraction having ad-- mixed therewith a minor proportion of a' mixture of aromatic condensation products comprising wherein the carboxyl'hydrogen is replaced with its equivalent weight of metal; and in each of which at least one other nuclear hydrogen atom of said characterizing aromatic nucleus is substituted with an aliphatic hydrocarbon radicalderived from petroleum wax, the radicals-derived from petroleum wax being predominantly radicals of at least 20 carbon atoms.

9. An improved mineral oil composition comprising a viscous mineral oil fraction having admixed therewith a minor proportion of an aromatic condensation product comprising anare matic nucleus in whichat least one nuclear hy drogen atom is substituted witharadicalselccted from the group consisting of aliphatic and cycloaliphatic carboxylic acid. radicals wherein the carboxyl hydrogen is replaced-with its equivalent weight of metal; and in which at least. oneothernuclear hydrogen atom of said characterizing aromatic nucleusissubstitutedwith analiphatic hydrocarbon radical of at least twenty carbon atoms, and at least one other hydrogen atom of said characterizing aromatic nucleus being substituted with a radical selected from the group consisting of hydroxy, alkoxy, aroxy, aralkyl, aryl, alkaryl, halogen, nitro, amino and organic ester radicals and alkyl radicals containing less than twenty carbon atoms.

10. An improved mineral oil composition comprising a viscous mineral oil fraction having admixed therewith a minor proportion of an arcmatic condensation product comprising an aromatic nucleus in which at least one nuclear hydrogen atom is substituted with a radical selected from the group consisting of aliphatic and cycloaliphatic carboxylic acid radicals wherein the carboxyl hydrogen is replaced with its equivalent weight of metal; and in which at least one other nuclear hydrogen atom of said characterizing aromatic nucleus islsubstituted with an aliphatic hydrocarbon radical of at least twenty carbon atoms, and at least one other hydrogen atom of said characterizing aromatic nucleus being substituted with a hydroxyl radical.

11. An improved mineral oil composition comprising a viscous mineral oil-fraction having admixed therewith a minor proportion of a mixture of aromatic condensation products comprising aromatic nuclei in each of which at least one nuclear hydrogen atom is substituted with a radical selected from the group consisting of aliphatic and cyclo-aliphatic carboxylic acid radicals wherein the carboxyl hydrogen is replaced with its equivalent weight of metal; and in each of which at least one other nuclear hydrogen atom ofsaid characterizing aromatic nucleus is substituted with an aliphatic hydrocarbon radical derived from petroleum wax, and at least one other hydrogen-atom of said characterizing aromatic nucleus is substituted with a hydroxyl rad ical, the radicals derived from petroleum wax being predominantly radicals of at least 20 carbon atoms.

12I An improved mineral oil composition comprising a viscous mineral oilfraction having-admixed therewith a minor proportion of an arcmatic condensation compound consisting of an aromatic nucleus in which at least one nuclear hydrogen atom is substituted with a radical selected from the group consisting of aliphatic and cyclo-aliphatic carboxylic acid radicals wherein the carboxyl hydrogenis substituted with its equivalent weight of metal, the' radical of said first mentioned groupcontaining. at least. one substituent selected from the group consisting of alkyl, aralkyl, alkaryl, aryl, keto, ether, hydroxyl,

halogen, nitro and amino radicals; and in which.

at least one other hydrogen atom of the said aromatic nucleus is substituted with an aliphatic hydrocarbon radical containing at least twenty carbon atoms.

13. An improved mineral oil composition comprising a viscous mineral oil fractionv having admixed therewith a minor proportion of an aromatic condensation compound consisting of an aromatic nucleus in which at least one nuclear hydrogen atom is substituted with a radical selected from the group consisting of aliphatic and,

cycle-aliphatic carboxylic acid radicals wherein the carboxyl hydrogen is substituted with its equivalent weight of metal, the radical of said first mentioned group containing at least one substituent selected from the group consisting of alkyl, aralkyl, alkaryl, aryl, keto, ether, hydroxyl, halogen, nitro and amino radicals; and in which at least one other hydrogen atom of the said aromatic nucleus is substituted with an aliphatic hydrocarbon radical containing, at least twenty carbon atoms, at least one other hydrogen atom of said aromatic nucleus being substituted with a radical selected from the group consisting of hydroxy, alkoxy, aroxy, aralkyl, aryl, alkaryl, halogen, nitro, amino and organic ester radicals and alkyl radicals containing less than twenty carbon atoms.

14. An improved mineral oil composition comprising a viscous mineral oil fraction having admixed. therewith a minor proportion of an aromatic condensation compound consisting of an aromatic nucleus in which at least one nuclear I V-I vvu-- hydrogen atom is substituted with a radical selected from the group consisting of aliphatic and cycloaliphatic carboxylig acid, radicals wherein the carboxyl hydrogen is substituted with its equivalent weight of metal, the radical of said first mentioned group containing at least one substituent selected from the group consisting of alkyl, aralkyl, alkaryl, aryl, keto, ether, hydroxyl, halogen, nitro and amino radicals; and in which at least one other hydrogen atom of the said aromatic nucleus is substituted with an aliphatic hydrocarbon radical containing at least twenty carbon atoms; at least one other hydrogen atom of said characterizing aromatic nucleus being substituted with a hydroxyl radical.

15. An improved mineral oil composition comprising a viscous mineral oil fraction having admixed therewith a minor proportion of the metal salt of an alkyl-substituted aryl-stearic acid in which the alkyl substituent contains at least twenty carbon atoms and is attached to the aryl nucleus.

16. An improved mineral oil composition comprising a viscous mineral oil fraction having admixed therewith a minor proportion of the metal salt of an alkyl-substituted aryl-succinic acid in which the alkyl substituent contains at least twenty carbon atoms and is attached to the aryl nucleus.

17. An improved mineral oil composition comprising a viscous mineral oil fraction having admixed therewith a minor proportion of the metal salt of an alkyl-substituted aryl-acetic acid in which the alkyl substituent contains at least twenty carbon atoms 'andis'atta'chedto the aryl nucleus.

18. An improved mineral oil composition comprising a viscous mineral oil fraction and in admixture therewith a minor proportion of a metal salt of an alkyl-substituted aromatic-aliphatic carboxylic acid in which the alkyl substituent contains at least twenty carbon atoms and is attached to the aromatic nucleus and in which the metal element of said salt is a polyvalent metal.

19. An improved mineral oil composition comprising a viscous mineral oil fraction and in admixture therewith a minor proportion of an oilmiscible metaloreanic compound having the general formula R T(Z.COOM)Yb)n, in which: T represents an aromatic nucleus; Z represents an organic radical attached to the nucleus T; COOM represents at least one carboxyl group attached to the radical Z, the carboxyl hydrogen thereof being replaced by its equivalent weight of a metal M; R, represents at least one aliphatic hydrocarbon radical of at least twenty carbon atoms having a valence v of from one to four and attached by one valence bond only to at least one nucleus T; Yb represents a monovalent radical attached to T and selected from the group consisting of residual hydrogen and hydroxy, alkoxy, aroxy, aralkyl, aryl, alkaryl, halogen, nitro, amino and organic ester radicals and alkyl radicals containing less than twenty carbon atoms; b represents the number of Ybs and is equal to zero or a whole number corresponding to the replaceable hydrogens on the nucleus I not substituted with R and (ZCOOM); and n is a whole number from 1 to 4.

20. An improved mineral oil composition comprising a viscous mineral oil fraction and in ad mixture therewith a minor proportion of an oilmiscible metalorganic compound having the general formula R (T(ZlCOOM)Yb)n, in which: T

represents an aromatic nucleus; Z represents an alkyl radical selected from the group consisting of aliphatic and cyclo-aliphatic hydrocarbon radicals, said alkyl radical Z being attached to the nucleus T; COOM represents at least one carboxylate group containing a metal M and attached to the alkyl radical Z; R represents at least one aliphatic hydrocarbon radical of at least twenty carbon atoms and having a valence v of from one to four and attached by one valence bond only to at least one aromatic nucleus T; Yb represents a monovalent radical attached to T and selected from the group consisting of residual hydrogen and hydroxy, alkoxy, aroxy, aralkyl, aryl, alkaryl, halogen, nitro, amino and organic ester radicals and alkyl radicals containing less than twenty carbon atoms; b represents the number of Ybs and is equal to zero or a whole number corresponding to the replaceable hydrogens on the nucleus '1 not substituted with R and (Z.COOM) and n is a whole number from 1 to 4.

21. An improving agent for mineral oils comprising the metal salt of an alkyl-substituted aromatic-aliphatic carboxylic acid in which the alkyl substituent contains at least twenty carbon atoms and is attached to the aromatic nucleus.

22. An improving agent for mineral oils comprising the metal salt of an alkyl-substituted aromatic-aliphatic carboxylic acid in which the alkyl substituent contains at least twenty carbon atoms and is attached to the aromatic nucleus, the said aromatic nucleus containing at least one substituent selected from the group consisting of hydroxy, alkoxy, aroxy, aralkyl, aryl, alkaryl, halogen. nitro, amino *and'organic ester radicals and alkyl radicals containing less than twenty carbon atoms.

23. An improving agent for mineral oils comprising a metalorganic condensation product consisting of an aromatic nucleus in which at least one nuclear hydrogen atom is substituted with a radical selected from the group consisting of aliphatic and cyclo-aliphatic carboxylic acid radicals wherein the carboxyl hydrogen is replaced with its equivalent weight of metal, and in which at least one other nuclear hydrogen atom of said characterizing aromatic nucleus is substituted with an aliphatic hydrocarbon radical of at least twenty carbon atoms.

24. An improving agent for mineral oils comprising a mixture of metalorganic condensation products consisting of aromatic nuclei in each of which at least one nuclear hydrogen atom is substituted with a radical selected from the group consisting of aliphatic and cyclo-aliphatic carboxylic acid radicals wherein the carboxyl hydrogen is replaced with its equivalent weight of metal, and in each of which at least one other nuclear hydrogen atom of said characterizing aromatic nucleus is substituted with an aliphatic hydrocarbon radical derived from petroleum wax, the radicals derived from petroleum wax being predominantly radicals of at least 20 carbon atoms.

25. An improving agent for mineral oils comprising a metalorganic condensation product consisting of an aromatic nucleus in which at least one nuclear hydrogen atom is substituted with a radical selected from the group consisting of aliphatic and cyclo-aliphatic carboxylic acid radicals wherein the carboxyl hydrogen is replaced with its equivalent weight of metal, and in which at least one other nuclear hydrogen atom of said characterizing aromatic nucleus is substituted with an aliphatic hydrocarbon radical of at least twenty carbon atoms; at least one other hydrogen atom of said. characterizing aromatic nucleus being substituted with a radical selected from the group consisting of hydroxy, alkoxy, aroxy, aral kyl, aryl, alkarylQhalogen, nitro, amino and organic ester radicals and alkyl radicals containing less than twenty carbon atoms.

26. An improving agent for mineral oils com prising a metalorganic condensation product consisting of an aromatic nucleus in which at least one nuclear hydrogen atom is substituted with a radical selected from the group consisting of aliphatic and cyclo-aliphatic carboxylic acid radicals wherein the carboxyl hydrogen is substituted with its equivalent weight of metal, the radical of said first mentioned group containing at least one substituent selected from the group consisting of alkyl, aralkyl, alkaryl, aryl, keto, ether, hydroxy, halogen, nitro and amino radicals; and in which at least one other hydrogen atom of the said characterizing aromatic nucleus is substituted with an aliphatic hydrocarbon radical containing at least twenty carbon atoms.

27. An improving agent for mineral oils comprising a metalorganic condensation product consisting of an aromatic nucleus in which at least one nuclear hydrogen atom is substituted with a radical selected from the group consisting of a1iphatic and cycle-aliphatic carboxylic acid radicals wherein the carboxylic hydrogen is substituted with its equivalent weight of metal, the radical of said first mentioned group containing at least one substituent selected from the group consisting of alkyl, aralkyl, alkaryl, aryl, keto, ether,

hydroiqrl halogen nitro and amino-radicalsgand in which at least one other hydrogen atom of the said characterizing aromatic nucleus is substituted with an aliphatic hydrocarbon radical containing at least twenty carbon atoms; at least one other hydrogen atom of said aromatic nucleus being substituted with a radical selected from the group consisting of hydroxy, alkoxy, aroxy, aralkyl, aryl, alkaryl, halogen, nitro, amino and organic ester radicals and alkyl radicals containing less than twenty carbon atoms.

28. An improving agent for mineral oils comprising a mixture of metal organic condensation products consisting of aromatic nuclei in each of which at least one nuclear hydrogen atom is substituted with a radical selected from the group consisting of aliphatic and cyclo-aliphatic carbcxylic acid radicals in which the carboxyl hy* drogen is replaced with its equivalent weight of metal, and in each of which at least one other nuclear hydrogen atom of said aromatic nucleus is substituted with an aliphatic hydrocarbonradical derived from petroleum wax; at least one other nuclear hydrogen atom of said aromaticnucleus being substituted with an'hydroxyl radical, the radicals derived from petroleum wax being predominantly radicals of at least 20 carbon atoms.

29. An improving agent for mineral oils comprising a metalorganic compound having the general formula R (T(Z.COOM) Yb) n, in which T represents an aromatic nucleus; Z represents an or-' ganic radical attached to the nucleus T; COOM represents at least one carboxyl group attached to the radical Z, the carboxyl hydrogen thereof being replaced by its equivalent weight of a metal M; R represents at least one aliphatic hydrocarbon radical of at least 20 carbon atoms having a valence v of from 1 to 4 and attached by one valence bond only to at least one nucleus T; Yb represents a monovalent radical attachedto T and selected from the group consisting of residual hydrogen and hydroxy, alkoxy, aroxy, aralkyl, aryl, alkaryl, halogen, nitro, amino and organic ester radicals and alkyl radicals containing less than twenty carbons atoms; b represents the number of Ybs and is equal to zero or a whole number corresponding to the replaceable hydrogens on the nucleus T not substituted with R and (if-COOM); and n is a whole number from 1 to 4.

30. An improving agent for mineral oils'comprising a metalorganic compound having the general formula R"(T(Z.CM)'Yb)1r, in'which'z' T' represents an aromatic nucleus; Z represents an alkyl radical selected fromlthe groups consisting of aliphatic and cycle-aliphatic hydrocarbonrad- T; COOM represents at' least one carboxylate group containing a metal M and attached to the alkyl radical'Z; R" represents at least one aliphatic hydrocarbon radical of at least carbon atoms having a valence v of from '1 to 4 and attached by one valence bond only touat least one nucleus T; Yb represents a monovalent radical attached to T and selected from the group consisting of residual hydrogen and hydroxy, alkoxy, aroxy, aralkyl, aryl, alkaryL'halogen, nitro, amino and organic ester radicals and alkyl radicals containing less than twenty carbon atoms; b represents the number of Ybs and is equal to zero or a whole number corresponding to the replaceable --ieals-,- said-radical%beingzattached'to the nucleus hydrogens ,on the nucleus T' not substituted with JOHN J. GIAMlVIARIA.

phi/gang QBERRIGHT'.

, CERTIFICATE OF CORRECTION. Patent no. 2,198,275. April 2;, 191m.

03mm) 14. REIFF, ET AL.

It is. hereby certified that error appears in the printedspecification of the above numbered patent requiringi'correction as followsi Page 1, second column, line 6, for the word "in" read --to--'; page 2, first column,

"line 1+7, for chain chain read --chain-; page 6 first column, line 58- 59, for "hjdroxy' read --hydroxy-aryl-- line 14.0, for "waxy-f reed --wax line 72;, for "preferably" read preferab1e-'; .page 10, first column, line -25',' fer "eorboxylic" read carboxylic--; page 11, first col'umn, line k9, claim '19, for that portion of the for-mule. reading "E ER" read --R (T--; and theit the said Letters Patent should be read with this correction therein that the senie .may conform to the record of the ease in the Patent Office.

Signed and sealed this 25th day'ef March, A, D. 19141.

Henry Van Arsdale, (Seal) Acting Commissioner of Patents. 

